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The prevalence of opioid use during pregnancy is increasing. Two downstream effects are neonatal abstinence syndrome (NAS), a postnatal withdrawal syndrome, and long-term prenatal opioid exposure (LTPOE) without documented withdrawal symptoms in the infant. Mental health characteristics of mothers of infants with NAS and LTPOE have not been described. Using linked maternal and infant Medicaid claims and birth certificate data, we analyzed 15,571 infants born to Medicaid-insured women 15–24 years old in a mid-Atlantic city from 2007 to 2010. Pairwise comparisons with multinomial logistic regression, adjusting for maternal and infant covariates, were performed. We compared four mental health conditions among mothers of infants with NAS, infants with LTPOE without NAS, and controls: depression, anxiety, bipolar disorder, and schizophrenia. The prevalence of depression among mothers of infants with NAS, infants with LTPOE, and controls was 26, 21.1, and 5.5% respectively. Similar results were found for anxiety. In multivariable analysis, mothers of infants with NAS and LTPOE had approximately twice the depression risk as controls, while mothers of infants with LTPOE had 2.2 times the bipolar disorder risk and 4.6 times the schizophrenia risk as controls. The overall risk of mental health conditions in mothers of infants with NAS and LTPOE was similar. Mothers of infants with LTPOE who did not develop NAS are at similarly high risk for mental health conditions as mothers of infants with NAS, and both are at higher risk than controls. Therefore, those mothers of infants who did not develop symptoms of NAS despite LTPOE may be a vulnerable population that needs additional mental health support in the post-partum period.